WO2019008801A1 - Dispersant pour liquide de revêtement d'électrode, composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, et un dispositif de stockage d'énergie comprenant une électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour un liquide de revêtement d'électrode - Google Patents

Dispersant pour liquide de revêtement d'électrode, composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, et un dispositif de stockage d'énergie comprenant une électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour un liquide de revêtement d'électrode Download PDF

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Publication number
WO2019008801A1
WO2019008801A1 PCT/JP2018/002045 JP2018002045W WO2019008801A1 WO 2019008801 A1 WO2019008801 A1 WO 2019008801A1 JP 2018002045 W JP2018002045 W JP 2018002045W WO 2019008801 A1 WO2019008801 A1 WO 2019008801A1
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WO
WIPO (PCT)
Prior art keywords
coating liquid
electrode
electrode coating
storage device
cellulose fiber
Prior art date
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PCT/JP2018/002045
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English (en)
Japanese (ja)
Inventor
綾乃 祖父江
恭輝 齊藤
洋介 後居
圭樹 伊藤
哲也 東崎
悠司 星原
真昌 松本
Original Assignee
第一工業製薬株式会社
エレクセル株式会社
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Application filed by 第一工業製薬株式会社, エレクセル株式会社 filed Critical 第一工業製薬株式会社
Priority to US16/624,912 priority Critical patent/US11437607B2/en
Priority to CN201880042055.5A priority patent/CN110896675B/zh
Priority to KR1020197037165A priority patent/KR102503911B1/ko
Publication of WO2019008801A1 publication Critical patent/WO2019008801A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/604—Polymers containing aliphatic main chain polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a dispersant for electrode coating liquid, an electrode coating liquid composition containing the dispersant for electrode coating liquid, an electrode for a power storage device manufactured using the electrode coating liquid composition, and the power storage device.
  • the present invention relates to a power storage device provided with a device electrode.
  • a power storage device having a high voltage and a high energy density has been required as a power supply for driving an electronic device.
  • lithium ion secondary batteries, lithium ion capacitors and the like are expected as high voltage, high energy density storage devices.
  • an electrode used for a storage device is usually manufactured by applying and drying a mixture of electrode active material particles, conductive material particles, and a binder on the surface of a current collector.
  • the storage device include a lithium ion secondary battery, an electric double layer capacitor, and a lithium ion capacitor.
  • These power storage devices are mainly composed of members such as an electrode, a non-aqueous electrolyte, and a separator.
  • an electrode for a storage device is, for example, applying an electrode mixture solution for a storage device, in which an electrode active material and a conductive material are dispersed in an organic solvent or water together with a binder, on a metal foil as a collector surface. It is formed by drying.
  • the characteristics of the electricity storage device depend, of course, largely on the main constituent materials such as the electrode particle material, electrolyte, and current collector used, but the binder, thickening stabilizer, and dispersant used as additives It also depends greatly on.
  • the binder for a storage battery device is mainly divided into an organic solvent based binder in which a polymer is dissolved in an organic solvent and an aqueous binder in which a polymer is dissolved or dispersed in water.
  • an electrode mixture for a water-based storage device using a water-based binder has attracted attention because it can reduce the environmental load and production cost and can improve the working environment.
  • electrode materials such as electrode active materials and conductive materials are being made into nanomaterials along with the increase in capacity and energy of batteries.
  • the dispersion stabilizer is added for the purpose of dispersing and stabilizing the electrode active material and the conductive material, and imparting a viscosity suitable for coating the electrode coating liquid.
  • a water-soluble polymer is used as a dispersion stabilizer, and among them, carboxymethyl cellulose salt is excellent in dispersion stability and is often used.
  • Patent Document 1 Patent Document 2
  • the dispersion stability may be insufficient, the dispersion stabilization may take a long time, or the coating failure of the electrode coating liquid There was a problem such as
  • the electrode active material is dispersed by mixing the electrode active material, the thickening / stabilizing agent, the dispersion medium, and other components to produce an electrode coating liquid.
  • a mixing / dispersing machine having a large dispersing ability.
  • the present invention is a dispersion agent for an electrode coating liquid, which is excellent in the dispersion stability of the electrode active material and the conductive material, and which can form a uniform electrode coating liquid composition even if a dispersing apparatus with weak shear force is used, It is an object of the present invention to provide an electrode coating liquid composition containing the above, an electrode for a storage device manufactured using the same, and a storage device provided with the electrode for the storage device.
  • the present inventors are to obtain a dispersant for an electrode coating liquid which is excellent in the dispersion stability of the electrode active material and the poorly dispersed conductive auxiliary agent, and which can produce a uniform electrode even with a weak shear dispersion device.
  • a dispersant for electrode coating liquid which comprises a cellulose fiber satisfying the following (a) to (c).
  • the number average width of the short width is 2 nm to 200 nm
  • the aspect ratio is 7.5 to 250
  • cellulose I-type crystal and the crystallinity is 70% to 95%
  • the anionic functional group is a carboxyl group, and the content of the carboxyl group is 1.2 mmol / g or more and 2.5 mmol / g or less
  • An electrode coating composition comprising the electrode coating composition dispersant as described in any one of [1] to [3].
  • the content of the above-mentioned cellulose fiber is 0.05 mass% or more and 5.00 mass% or less with respect to 100 mass% of the solid content of the coating liquid composition for an electric storage device [4]
  • An electrode for a storage battery device comprising the dried product of the composition for an electrode coating liquid according to [4] or [5].
  • a storage device comprising the storage device electrode described in [6].
  • the dispersant for electrode coating liquid of the present invention can be obtained by uniformly dispersing the electrode material by the high dispersion stability effect, thereby obtaining an electrode coating liquid composition without bias and an electrode made therefrom. Since the electricity storage device has high electron conductivity and accordingly low internal resistance, it has the effect of increasing battery performance.
  • the dispersing agent for an electrode coating liquid of the present invention is weak because of its excellent dispersing effect, without requiring a strong mechanical dispersing operation which has conventionally been required for uniform dispersion of the electrode coating liquid composition. Uniform dispersion of the electrode coating liquid composition is possible with a simple mechanical dispersing device having a shearing force.
  • the dispersant for electrode coating liquid of the present invention contains a predetermined cellulose fiber.
  • the above-mentioned cellulose fiber has a number average width of 2 nm or more and 200 nm or less in the short width. If the number average width of the short width is less than 2 nm, the dispersion stability may be deteriorated, and if it exceeds 200 nm, the dispersion ability may be reduced.
  • the number average width can be measured by the following method. That is, an aqueous dispersion of fine cellulose fibers with a solid content of 0.05 to 0.1% by mass is prepared, and the dispersion is cast on a hydrophilized carbon film-coated grid to obtain transmission electron Let it be a sample for observation of a microscope (TEM). Then, observation with an electron microscope image is performed at a magnification of 5000 times, 10000 times or 50000 times depending on the size of the fibers to be constructed. At this time, an axis of an arbitrary image width in the vertical and horizontal directions is assumed in the obtained image, and the sample and observation conditions (such as magnification) are adjusted such that 20 or more fibers intersect with the axis.
  • TEM microscope
  • the above-mentioned cellulose fiber has an aspect ratio of 7.5 or more and 250 or less, more preferably 25 or more and 75 or less. If the arpect ratio is less than 7.5, the dispersibility of the electrode material may be insufficient. If it exceeds 250, a strong shearing force is required for the dispersion of the electrode material, which may damage the electrode material. There is.
  • the aspect ratio of the above-mentioned cellulose fiber can be measured, for example, by the following method, that is, after casting cellulose on a hydrophilized carbon film-coated grid, a TEM image (magnification of magnification) negatively stained with 2% uranyl acetate
  • the number average width of the short width of the cellulose fiber and the number average width of the long width were observed from 10000 times). That is, the number average width of the short width and the number average width of the long width were calculated according to each of the methods described above, and the aspect ratio was calculated according to the following equation (1) using these values. .
  • Aspect ratio number average width (nm) of the long width side / number average width (nm) of the short width side (1)
  • the cellulose fiber has cellulose type I crystals, and the degree of crystallinity is 70% or more. When the degree of crystallinity is less than 70%, the characteristics derived from the cellulose crystal structure can not be expressed, and the dispersibility of the electrode material may be insufficient.
  • the degree of crystallinity may more preferably be 80% or more.
  • the upper limit of the degree of crystallinity is not particularly limited, but is preferably 95% or less, more preferably 92% or less, from the viewpoint of the shear force required for the dispersion of the electrode material.
  • the crystallinity degree of cellulose is a cellulose type I crystallinity degree calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following formula (2).
  • Cellulose type I crystallinity (%) [(I 22.6 ⁇ I 18.5 ) / I 22.6 ] ⁇ 100 (2)
  • cellulose I type is a crystal form of natural cellulose
  • cellulose I type crystallinity means the ratio for which the amount of the crystal region occupies in the whole cellulose.
  • the cellulose fiber can be produced by a known method. Although not particularly limited, specifically, for example, it can be obtained by suspending natural cellulose fiber in water and treating it with a high-pressure homogenizer, grinder or the like to make it finer.
  • the natural cellulose fiber is not particularly limited as long as it is a plant or animal, or a cellulose fiber derived from a microorganism, and kraft pulp or dissolved pulp derived from softwood or hardwood, cotton linter, lignocellulose having low cellulose purity, wood flour, grass cellulose, Bacterial cellulose etc. are mentioned.
  • the said cellulose fiber can use the bacterial cellulose fiber produced by bacteria.
  • the bacteria include Acetobacter (Acetobacter) genus and the like, and more specifically, Acetobacter aceti (Acetobacter aceti), Acetobacter subsp., Acetobacter xylinum etc. It can be mentioned.
  • Acetobacter Acetobacter
  • Aceti Acetobacter aceti
  • Acetobacter subsp. Acetobacter xylinum etc. It can be mentioned.
  • cellulose is produced from the bacteria.
  • the resulting product contains bacteria and cellulose fibers (bacterial cellulose) produced from the bacteria and linked to the bacteria, so this product is removed from the culture medium, washed with water, or treated with an alkali, etc. By removing the bacteria, it is possible to obtain water-containing bacterial cellulose free of bacteria.
  • the above-mentioned cellulose fiber can maintain I-type crystal structure, and from the viewpoint of being able to fibrillate efficiently to a predetermined fiber diameter, it is a cellulose fiber having an anionic group preferable.
  • the anionic group is not particularly limited, and examples thereof include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, a sulfuric acid group, or a salt of these groups, and any one of these groups is included. And may have two or more. Moreover, you may have a coupling group between the glucose unit which comprises cellulose, and the said anionic group.
  • the salt of the anionic group is not particularly limited, and examples thereof include alkali metal salts such as sodium salt, potassium salt and lithium salt, alkaline earth metal salts such as magnesium salt, calcium salt and barium salt, ammonium salt and phosphonium salt Amine salts such as onium salts, primary amines, secondary amines, tertiary amines and the like can be mentioned.
  • alkali metal salts such as sodium salt, potassium salt and lithium salt
  • alkaline earth metal salts such as magnesium salt, calcium salt and barium salt
  • Amine salts such as onium salts, primary amines, secondary amines, tertiary amines and the like can be mentioned.
  • the anionic group includes an acid type such as carboxylic acid group, phosphoric acid group, sulfonic acid group and sulfuric acid group, and a salt type such as carboxylic acid group, phosphoric acid group, sulfonic acid group and sulfuric acid base
  • a preferred embodiment is that it contains a salt type anionic group, a cellulose fiber having only a salt type anionic group may be used, and a salt type anionic group and an acid type anion You may use the cellulose fiber in which the sex group is mixed.
  • an oxidized cellulose formed by oxidizing a hydroxyl group of a glucose unit constituting the cellulose is exemplified to be described more specifically, and a manufacturing method An example is also described.
  • the oxidized cellulose is not particularly limited, but it is preferable that the 6-position hydroxyl group of the glucose unit be selectively oxidized. It can be confirmed, for example, by a 13 C-NMR chart that the oxidized cellulose is a selectively oxidized hydroxyl group at the 6-position on the glucose unit.
  • the oxidized cellulose may have an aldehyde group or a ketone group together with a carboxylic acid group (COOH) and / or a carboxylic acid group (COOX, wherein X represents a cation forming a salt with the carboxylic acid). Is preferably substantially free of an aldehyde group and a ketone group.
  • the content (hereinafter referred to as the carboxyl group weight) of the carboxylic acid group of the cellulose fiber is preferably 1.2 mmol / g or more and more preferably 1.5 mmol / g or more. Moreover, 2.5 mmol / g or less is preferable, More preferably, it is 2.0 mmol / g or less. When the amount of carboxyl groups is in the above range, the dispersibility of the electrode material becomes good.
  • the amount of carboxyl groups of the above-mentioned cellulose fiber is measured, for example, by preparing 60 mL of a 0.5 to 1% by mass slurry from a cellulose sample whose dry mass is precisely weighed, and adjusting the pH to about 2.5 with 0.1 M aqueous hydrochloric acid After that, a 0.05 M aqueous solution of sodium hydroxide is dropped to conduct electrical conductivity measurement. The measurement is continued until the pH is about 11. From the amount of sodium hydroxide (V) consumed in the step of neutralization of a weak acid in which the change in electrical conductivity is gradual, the amount of carboxyl groups can be determined according to the following formula (3).
  • Carboxyl group content (mmol / g) V (mL) ⁇ [0.05 / cellulose mass] (3)
  • adjustment of the amount of carboxyl groups can be performed by controlling the addition amount and reaction time of the co-oxidant used by the oxidation process of a cellulose fiber so that it may mention later.
  • the above-mentioned oxidized cellulose fiber uses natural cellulose fiber as a raw material, uses N-oxyl compound as an oxidation catalyst in water, and reacts with a co-oxidant to oxidize the natural cellulose fiber to obtain a reaction product (1) It can be obtained by a manufacturing method including a purification step (2) to obtain a reactant impregnated with water by removing impurities and a dispersion step (3) to disperse the reactant impregnated with water in a solvent.
  • (1) Oxidation Reaction Step After the natural cellulose fiber and the N-oxyl compound are dispersed in water (dispersion medium), a co-oxidant is added to start the reaction. During the reaction, 0.5 M aqueous sodium hydroxide solution is added dropwise to keep the pH at 10 to 11, and when no change is observed in the pH, the reaction is regarded as complete.
  • the co-oxidant is not a substance that directly oxidizes a cellulose hydroxyl group, but a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
  • the above-mentioned natural cellulose fiber means a purified cellulose fiber isolated from a biosynthetic system of cellulose such as plant, animal and bacteria-produced gel. More specifically, cotton pulp such as softwood pulp, hardwood pulp, cotton linter and cotton lint, non-wood pulp such as straw pulp and bagasse pulp, bacterial cellulose fiber (BC), and cellulose fiber isolated from sea squirt And cellulose fibers etc. isolated from seaweed. These may be used alone or in combination of two or more. Among these, softwood pulp, hardwood pulp, cotton linter such as cotton linters and cotton lint, non-wood pulp such as straw pulp and bagasse pulp are preferable.
  • the above-mentioned natural cellulose fiber is preferable because the reaction efficiency can be enhanced and the productivity can be enhanced by subjecting it to a treatment for increasing the surface area such as beating.
  • a treatment for increasing the surface area such as beating.
  • the reaction efficiency is enhanced. It is preferable because the number average fiber diameter after the refining treatment can be reduced.
  • the dispersion medium of the natural cellulose fiber in the above reaction is water, and the natural cellulose fiber concentration in the reaction aqueous solution is arbitrary as long as the reagent (natural cellulose fiber) can be sufficiently diffused.
  • the reaction concentration is about 5% or less based on the weight of the reaction aqueous solution, but the reaction concentration can be increased by using an apparatus with strong mechanical stirring power.
  • examples of the N-oxyl compound include compounds having a nitroxy radical generally used as an oxidation catalyst.
  • the above-mentioned N-oxyl compound is preferably a water-soluble compound, more preferably piperidine nitroxoxy radical, and in particular 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) or 4-acetamido-TEMPO preferable.
  • TEMPO 2,2,6,6-tetramethylpiperidinooxy radical
  • 4-acetamido-TEMPO preferable.
  • the addition of the N-oxyl compound is sufficient in a catalytic amount, preferably 0.1 to 4 mmol / L, more preferably 0.2 to 2 mmol / L, and added to the aqueous reaction solution.
  • Examples of the co-oxidant include hypohalogenous acid or a salt thereof, hypohalogenous acid or a salt thereof, perhalogenated acid or a salt thereof, hydrogen peroxide, perorganic acid and the like. These may be used alone or in combination of two or more. Among them, alkali metal hypohalites such as sodium hypochlorite and sodium hypobromous acid are preferable. And when using the said sodium hypochlorite, it is preferable to advance reaction in presence of alkali metal bromides, such as sodium bromide, from the point of reaction rate.
  • the addition amount of the above-mentioned alkali metal bromide is about 1 to 40 times by mole, preferably about 10 to 20 times by mole, with respect to the above-mentioned N-oxyl compound.
  • the pH of the reaction aqueous solution is preferably maintained in the range of about 8-11.
  • the temperature of the aqueous solution is optional at about 4 to 40 ° C., but the reaction can be carried out at room temperature (25 ° C.), and control of the temperature is not particularly required.
  • the degree of oxidation is controlled by the addition amount of the co-oxidant and the reaction time.
  • the reaction time is usually complete within about 5 to 120 minutes, at most 240 minutes. Also, by controlling the amount of co-oxidant added and the pH of the reaction aqueous solution, it is possible to control the degree of hydrolysis of cellulose molecules and to arbitrarily set the aspect ratio of cellulose fibers.
  • any device can be used as long as it can achieve the above-mentioned purpose, such as a method using centrifugal dehydration (for example, a continuous decanter).
  • the aqueous dispersion of reactant fibers obtained in this manner has a solid content (cellulose fiber) concentration in a squeezed state in the range of approximately 10% by mass to 50% by mass.
  • the solid content concentration is higher than 50% by mass, since very high energy is required for dispersion.
  • Dispersion process fine processing process
  • the reaction product (water dispersion) impregnated with water obtained in the above purification step is dispersed in a dispersion medium to carry out dispersion treatment.
  • the viscosity increases with the treatment, and a dispersion of finely divided cellulose fibers can be obtained.
  • the degree of the refinement processing for example, the treatment shear force of the dispersing machine, the treatment pressure, the number of treatments, the treatment time, etc.
  • the degree of the refinement processing for example, the treatment shear force of the dispersing machine, the treatment pressure, the number of treatments, the treatment time, etc.
  • the above-mentioned cellulose fiber may be dried if necessary.
  • the dispersion medium is water, spray drying, freeze drying, vacuum drying etc.
  • the dispersion medium is a mixed solution of water and an organic solvent
  • a drying method using a drum dryer, a spray drying method using a spray dryer, or the like is used. In addition, it does not interfere, without drying the dispersion of the said cellulose fiber in the state of a dispersion.
  • Dispersers used in the dispersion step include homomixers under high-speed rotation, high-pressure homogenizers, ultra-high pressure homogenizers, ultrasonic dispersion processors, beaters, disc refiners, conical refiners, double disc refiners, grinders, etc.
  • the use of a powerful and beating-capable device is preferred in that more efficient and advanced downsizing can be achieved, and a water-containing lubricant composition can be obtained economically and advantageously.
  • disperser examples include screw mixers, paddle mixers, disperser mixers, turbine mixers, dispersers, propeller mixers, kneaders, blenders, homogenizers, ultrasonic homogenizers, colloid mills, pebble mills, bead mills, and the like. It may be used. Also, two or more dispersers may be used in combination.
  • the above-mentioned cellulose fiber is preferably further subjected to a reduction reaction after the above-mentioned oxidation reaction.
  • the finely oxidized cellulose fiber after the oxidation reaction is dispersed in purified water, the pH of the aqueous dispersion is adjusted to about 10, and the reduction reaction is performed with various reducing agents.
  • the reducing agent to be used in the present invention general ones can be used, and preferably, LiBH4, NaBH3CN, NaBH4 and the like can be mentioned. Among them, NaBH 4 is preferable in terms of cost and availability.
  • the amount of the reducing agent is preferably in the range of 0.1 to 4% by mass, particularly preferably in the range of 1 to 3% by mass, based on the finely oxidized cellulose fiber.
  • the reaction is carried out at room temperature or at a temperature slightly higher than room temperature, usually for 10 minutes to 10 hours, preferably for 30 minutes to 2 hours.
  • the coating liquid for electrodes of the electricity storage device of the present invention contains the above-mentioned cellulose fiber as a dispersion stabilizer as a dispersion stabilizer.
  • content of the said cellulose fiber is 0.05 mass% or more and 5.00 mass% or less with respect to solid content 100 mass% of the coating liquid composition for electrical storage devices, More preferably, it is 0.1 mass% More than 2.0 mass% or less.
  • content of the cellulose fiber is less than 0.05% by mass, the dispersion stability is deteriorated, and when it exceeds 5.00% by mass, the internal resistance of the battery is increased, and the paint has high thixotropy. As a result, there is a problem that the preparation of the paint becomes difficult.
  • the mixing ratio of the above-mentioned cellulose fiber to other thickener and dispersion stabilizer is preferably in the range of 99: 1 to 50:50.
  • the content of the cellulose fiber and the other thickening / stabilizing agent is 0.2% by mass or more and 10.00% by mass or less with respect to 100% by mass of the solid content of the coating liquid composition for a storage battery device. Is preferred.
  • the thickener and dispersion stabilizer known ones can be used, and it is not particularly limited, but specifically, hydroxymethylcellulose, carboxymethylcellulose and alkali metal salts thereof, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxy Cellulose such as ethyl methyl cellulose; Polycarboxylic acid type compound such as polyacrylic acid and polyacrylic acid soda; Compound having vinyl pyrrolidone structure such as polyvinylpyrrolidone; Polyacrylamide, polyethylene oxide, polyvinyl alcohol, sodium alginate, sodium alginate, xanthan gum, carrageenan One or more selected from guar gum, agar, starch and the like can be used. Among them, carboxymethylcellulose salts can be suitably used.
  • the high molecular compound which has water solubility and / or water dispersibility is mentioned,
  • polyvinylidene fluoride poly fluoride
  • Polyvinylidene fluoride copolymer resin such as copolymer of vinylidene and hexafluoropropylene, perfluoromethyl vinyl ether and tetrafluoroethylene
  • fluorocarbon resin such as polytetrafluoroethylene and fluororubber
  • styrene-butadiene rubber ethylene-propylene Rubber
  • polymers such as styrene-acrylonitrile copolymer polyurethane resin, acrylic resin, polyester resin, polyimide resin, polyamide resin, and water dispersion such as epoxy resin
  • binders may be used alone or in combination of two or more types, or two or more types of resin composite types.
  • Examples of the electricity storage device of the present invention include known electricity storage devices, but are not particularly limited. Specific examples thereof include lithium secondary batteries and lithium ion capacitors.
  • the positive electrode active material used for the positive electrode of the lithium secondary battery of the present invention is not particularly limited as long as lithium ions can be inserted and released.
  • Examples include metal oxides such as CuO, Cu 2 O, MnO 2 , MoO 3 , V 2 O 5 , CrO 3 , MoO 3 , Fe 2 O 3 , Ni 2 O 3 , CoO 3 , LixCoO 2 , LixNiO 2 Composite oxides of lithium and transition metal such as LixMn 2 O 4 and LiFePO 4 , metal chalcogenides such as TiS 2 , MoS 2 and NbSe 3 , conductive polymers such as polyacene, polyparaphenylene, polypyrrole and polyaniline Compounds etc. may be mentioned.
  • complex oxides of at least one selected from transition metals such as cobalt, nickel, manganese, etc. which are generally called high voltage systems, and lithium are preferable from the viewpoint of easy release of lithium ions and high voltage.
  • the lithium composite oxide may be doped with a small amount of an element such as fluorine, boron, aluminum, chromium, zirconium, molybdenum, iron or the like, or the surface of the lithium composite oxide particles may be carbon, MgO, Al 2 O 3, those surface-treated with SiO 2 or the like can be used.
  • the positive electrode active material can be used in combination of two or more.
  • any known active material can be used without particular limitation as long as it can insert / eliminate metal lithium or lithium ion.
  • carbon materials such as natural graphite, artificial graphite, non-graphitizable carbon, and graphitizable carbon can be used.
  • metal lithium, metal alloy such as alloy, tin compound, lithium transition metal nitride, crystalline metal oxide, amorphous metal oxide, silicon compound, conductive polymer, etc. can be used, and specific examples are , Li 4 Ti 5 O 12 , NiSi 5 C 6 and the like.
  • an allotrope of carbon is usually used as an electrode active material used for an electrode for an electric double layer capacitor as the storage device of the present invention.
  • Specific examples of allotropes of carbon include activated carbon, polyacene, carbon whiskers and graphite, and powders or fibers thereof can be used.
  • a preferred electrode active material is activated carbon, and specific examples thereof include activated carbons that use phenol resin, rayon, acrylonitrile resin, pitch, coconut shell and the like as a raw material.
  • the electrode active material used for the lithium ion capacitor electrode of the present invention can reversibly carry lithium ions and anions such as tetrafluoroborate as the electrode active material used for the positive electrode of the lithium ion capacitor electrode. Anything is fine. Specifically, an allotrope of carbon is usually used, and an electrode active material used in an electric double layer capacitor can be widely used.
  • the electrode active material used for the negative electrode of the lithium ion capacitor electrode is a substance capable of reversibly supporting lithium ions.
  • an electrode active material used in the negative electrode of a lithium ion secondary battery can be widely used.
  • crystalline carbon materials such as graphite and non-graphitizable carbon, and the polyacene materials (PAS) described as the positive electrode active material can be mentioned. These carbon materials and PAS carbonize a phenol resin etc., are activated if necessary, and then crushed.
  • a conductive agent is used for the storage device electrode of the present invention as needed.
  • the conductive agent any electron conductive material which does not adversely affect the cell performance can be used.
  • carbon blacks such as acetylene black and kettin black are used, but natural graphite (scaly graphite, scaly graphite, earthy graphite etc.), artificial graphite, carbon whiskers, carbon fibers and metals (copper, nickel, aluminum, etc.)
  • It may be a conductive material such as silver, gold, etc.) powder, metal fiber, conductive ceramic material and the like. These can be used as 1 type, or 2 or more types of mixtures.
  • the addition amount thereof is preferably 0.1 to 30% by mass, particularly preferably 0.2 to 20% by mass, with respect to the mass of the active material.
  • any electron conductor which does not adversely affect the constructed battery can be used.
  • aluminum is used for the purpose of improving adhesion, conductivity and oxidation resistance.
  • a material obtained by treating the surface of copper or the like with carbon, nickel, titanium, silver or the like can be used.
  • the electrode of the electricity storage device of the present invention is, for example, in the form of a slurry by mixing an electrode active material, a conductive agent, a collector of the electrode active material, an electrode active material, and a binder for binding the conductive agent to the collector.
  • the electrode material of the invention is prepared and applied to an aluminum foil or copper foil as a current collector to volatilize the dispersion medium.
  • the method, sequence, etc. of mixing of the above electrode materials are not particularly limited.
  • the active material and the conductive agent can be mixed in advance, and in that case, a mortar, a mill mixer, a planetary ball mill Alternatively, a ball mill such as a shaker type ball mill, mechanofusion, or the like can be used.
  • a high shear disperser such as a high pressure homogenizer, an ultrahigh pressure homogenizer, a high speed rotary mixer, or a thin film swirl disperser can be used. The dispersibility of the electrode active material is further improved.
  • the present invention it is possible to use the active material and the conductive agent without mixing them in advance, and by using a self-revolution mixer and a high-speed homomixer in addition to the above method, a nanomaterial water dispersion having good storage stability. It is possible to make.
  • the excellent dispersion property of the above-mentioned cellulose makes it possible to prepare a nanomaterial water dispersion having good storage stability.
  • the nanomaterial is not limited to the active material and the conductive agent, and nanomaterials can be used.
  • the separator used in the electricity storage device of the present invention may be any separator used in ordinary electricity storage devices without particular limitation, and examples thereof include porous resins and ceramics made of polyethylene, polypropylene, polyolefin, polytetrafluoroethylene, etc. And non-woven fabrics.
  • the electrolytic solution used for the electricity storage device of the present invention may be an electrolytic solution used for an ordinary electricity storage device, and general ones such as an organic electrolytic solution and an ionic liquid can be used.
  • the electrolyte salt used in the storage device of the present invention include LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCl, LiBr, LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO) 2 ) 3 , LiI, LiAlCl 4 , NaClO 4 , NaBF 4 , NaI etc., and in particular, inorganic lithium salts such as LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 etc., LiN (SO 2 C x F 2x + 1 And organic lithium salts represented by (SO 2 CyF 2y + 1 ) can be mentioned.
  • x and y represent 0 or an integer of 1 to 4, and x + y is 2 to 8.
  • the organic lithium salt specifically, LiN (SO 2 F) 2 , LiN (SO 2 CF 3) (SO 2 C 2 F 5), LiN (SO 2 CF 3) (SO 2 C 3 F 7) , LiN (SO 2 CF 3) (SO 2 C 4 F 9), LiN (SO 2 C 2 F 5) 2, LiN (SO 2 C 2 F 5) (SO 2 C 3 F 7), LiN (SO 2 C 2 F 5 ) (SO 2 C 4 F 9 ) and the like.
  • LiPF 6 LiBF 4 , LiN (CF 3 SO 2 ) 2 , LiN (SO 2 F) 2 , LiN (SO 2 C 2 F 5 ) 2 or the like for the electrolyte because of excellent electric characteristics.
  • the electrolyte salt may be used singly or in combination of two or more. It is desirable that such a lithium salt be contained in the electrolytic solution usually at a concentration of 0.1 to 2.0 moL / L, preferably 0.3 to 1.5 moL / L.
  • the organic solvent for dissolving the electrolyte salt used in the electricity storage device of the present invention is not particularly limited as long as it is an organic solvent used for the non-aqueous electrolyte solution of the electricity storage device, for example, carbonate compound, lactone compound, ether compound, sulfolane Compounds, dioxolane compounds, ketone compounds, nitrile compounds, halogenated hydrocarbon compounds and the like can be mentioned.
  • carbonates such as dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol dimethyl carbonate, propylene glycol dimethyl carbonate, ethylene glycol diethyl carbonate, vinylene carbonate, lactones such as ⁇ -butyl lactone, Ethers such as dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, tetrahydropyran, 1,4-dioxane, sulfolanes, sulfolanes such as 3-methylsulfolane, dioxolanes such as 1,3-dioxolane, 4-methyl-2- Ketones such as pentanone, acetonitrile, nitriles such as pyrrolitonitrile, valeronitrile, bensonitrile etc., 1,2-di Halogenated hydrocarbons such as Roroetan, other
  • these mixtures may be sufficient.
  • organic solvents in particular, it is preferable to contain one or more nonaqueous solvents selected from the group consisting of carbonates, because the solubility, dielectric constant and viscosity of the electrolyte are excellent.
  • the electricity storage device of the present invention when used as a polymer electrolyte or polymer gel electrolyte, it is a polymer compound ether, ester, siloxane, acrylonitrile, vinylidene fluoride, hexafluoropropylene, acrylate, methacrylate, styrene, vinyl acetate, chloride
  • Polymers such as vinyl and oxetane or polymers having a copolymer structure or cross-linked polymers thereof may be mentioned.
  • the polymers may be of one type or two or more types.
  • the polymer structure is not particularly limited, but a polymer having an ether structure such as polyethylene oxide is particularly preferable.
  • a battery of a liquid type is an electrolytic solution
  • a battery of a gel type is a precursor solution in which a polymer is dissolved in an electrolytic solution
  • a solid electrolyte battery is a polymer container in which an electrolyte salt is dissolved.
  • the electricity storage device can be formed into a cylindrical, coin, square, laminate, or any other shape, and the basic configuration of the battery is the same regardless of the shape, and the design is changed according to the purpose. Can be implemented.
  • a wound body obtained by winding a negative electrode formed by applying a negative electrode active material to a negative electrode current collector and a positive electrode formed by applying a positive electrode active material to a positive electrode current collector through a separator. It can be obtained by storing it in a battery can, injecting a non-aqueous electrolyte, and sealing in a state where insulating plates are placed above and below.
  • a disk-shaped negative electrode, a separator, a disk-shaped positive electrode, and a stainless steel plate are stacked and stored in a coin-type battery can, and a non-aqueous electrolyte is injected and sealed. .
  • the temperature of the reaction solution was maintained at 10 ° C.
  • the reaction solution was neutralized by the addition of 0.1 N hydrochloric acid, and filtration and washing with water were repeated for purification to obtain a cellulose fiber having an oxidized fiber surface.
  • pure water was added to the above-mentioned cellulose fiber to dilute it to 1%, and cellulose fiber A-1 was produced by treating it once under a pressure of 100 MPa using a high pressure homogenizer (H11 manufactured by Sanwa Engineering Co., Ltd.).
  • Cellulose fiber A-2 was manufactured according to manufacture of cellulose fiber A-1 except the temperature of the reaction liquid in reaction being 20 degreeC, and having set pH 11.
  • Cellulose fiber A-4 was manufactured according to manufacture of cellulose fiber A-3 except the amount of addition of sodium hypochlorite aqueous solution having been 6.0 mmol / g to 1.0 g of the above-mentioned pulp.
  • Cellulose fiber A-5 was manufactured according to manufacture of cellulose fiber A3 except the amount of addition of sodium hypochlorite aqueous solution having been 9.0 mmol / g to 1.0 g of the above-mentioned pulp.
  • Cellulose fine particles were produced according to the method described in the example of JP-A-2003-73229. That is, first, a raw material pulp having a degree of polymerization of 760 obtained by cutting a sheet-like purified pulp into chips of 5 mm ⁇ 5 mm is dissolved in a 65 mass% aqueous sulfuric acid solution so that the cellulose concentration is 5 mass% at ⁇ 5 ° C. A clear and viscous cellulose dope was obtained. The cellulose dope was poured into 2.5 volumes of water (5 ° C.) while stirring to flocculate the cellulose into a floc to obtain a dispersion of floc solid.
  • This suspension is hydrolyzed at 85 ° C. for 20 minutes, and the sulfuric acid aqueous solution as the dispersion medium is removed by vacuum filtration using a glass filter, and then repeatedly repeatedly washed with water until the pH of the washing solution becomes about 3 Thereafter, the resultant was washed (neutralized) with a dilute aqueous ammonia solution having a pH of about 11, and further washed with ion-exchanged water to obtain a translucent white gel-like product having a cellulose concentration of 6.0% by mass.
  • the gel-like substance thus obtained is diluted with ion-exchanged water to prepare a cellulose concentration of 4.0% by mass, and a homomixer (TK Robomix, manufactured by Primix) is used.
  • Dispersion treatment was carried out at a rotational speed of 15,000 rpm for 10 minutes, followed by treatment 5 times at an operating pressure of an ultrahigh pressure homogenizer 140 MPa to produce cellulose fiber A'-1.
  • the number average width of the cellulose fiber was observed using a transmission electron microscope (TEM) (manufactured by JEOL Ltd., JEM-1400). That is, after casting each cellulose fiber onto a hydrophilized carbon film-coated grid, a short width is obtained according to the method described above from a TEM image (magnification: 10000 times) negatively stained with 2% uranyl acetate. The number average width of was calculated.
  • TEM transmission electron microscope
  • Aspect ratio number average width (nm) of the long width side / number average width (nm) of the short width side (1)
  • Carboxyl group content (mmol / g) V (mL) ⁇ [0.05 / cellulose mass] (3)
  • all of the celluloses A-1 to A-6 for the examples have an aspect ratio within the range of 7.5 to 250, with the number average width of the short width within the range of 2 to 200 nm. Met. Furthermore, the cellulose type I crystallinity was 70% or more. In contrast, cellulose A′-1 for the comparative example had a cellulose type I crystallinity of less than 70%. Cellulose A′-2 had a cellulose type I crystal structure, but both the number average width and the aspect ratio of the short width were at least the above range upper limit.
  • (Dispersion stabilizer) A-1 2% by mass aqueous dispersion of cellulose fiber A-1 A: 2% by mass aqueous dispersion of cellulose fiber A-2 A: 2% by mass aqueous dispersion A of cellulose fiber A-3 4: 2% by mass aqueous dispersion A-5 of cellulose fiber A-4: 2% by mass aqueous dispersion A-6 of cellulose fiber A-5: 2% by mass aqueous dispersion A ′ of cellulose fiber A-6 : 2% by mass aqueous dispersion A'-2 of cellulose fiber A'-1: 2% by mass aqueous dispersion B-1 of cellulose fiber A'-2: carboxymethylcellulose salt (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., WS- C) B-2: Carboxymethylcellulose salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., BSH-1)
  • C-1 Acetylene black (made by Denka Co., Ltd., HS-100)
  • C-2 Ketjen Black (manufactured by Lion Corporation, EC 600 JD)
  • C-3 Carbon black (Imeris, Super-P)
  • C-4 activated carbon (surface area: 1700 m 2 / g)
  • C-5 multilayer CNT (surface area: 230 m 2 / g)
  • Example 1 Add 99 parts by mass of C-1 as a conductive agent, 50 parts by mass of A-1 as a dispersion stabilizer (solid content: 1 part by mass), add water so that the total solid content is 6% by mass, and homodisper (prime mix)
  • the conductive agent water dispersion was produced by mixing for 90 minutes by the conditions of 1800 +/- 2000 rpm by TK ROBOMIX manufactured by the same company.
  • the degree of dispersion of the conductive agent was evaluated over time using a grind gauge (manufactured by Kotec Co., Ltd.).
  • Examples 2 to 34 Comparative Examples 1 to 18
  • a conductive agent water dispersion was prepared in the same manner as in Example 1 except that the type and amount of the conductive agent and the type and amount of the dispersion stabilizer were changed as shown in Table 1.
  • (Dispersion stabilizer) A-1 2% by mass aqueous dispersion of cellulose fiber A-1 A: 2% by mass aqueous dispersion of cellulose fiber A-2 A: 2% by mass aqueous dispersion A of cellulose fiber A-3 4: 2% by mass aqueous dispersion A-5 of cellulose fiber A-4: 2% by mass aqueous dispersion A-6 of cellulose fiber A-5: 2% by mass aqueous dispersion A ′ of cellulose fiber A-6 : 2% by mass aqueous dispersion A'-2 of cellulose fiber A'-1: 2% by mass aqueous dispersion B-1 of cellulose fiber A'-2: carboxymethylcellulose salt (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., WS- C) B-2: Carboxymethylcellulose salt (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., BSH-1) HEC: Hydroxyethy
  • C-1 Acetylene black (made by Denka Co., Ltd., HS-100)
  • C-2 Ketjen Black (manufactured by Lion Corporation, EC 600 JD)
  • C-3 Carbon black (Imeris, Super-P)
  • SBR styrene butadiene rubber water dispersion
  • PU-A polyurethane water dispersion (Daiichi Kogyo Seiyaku Co., Ltd .; Superflex 130)
  • PU-B Polyurethane water dispersion (Daiichi Kogyo Seiyaku Co., Ltd .; Superflex 420)
  • PU-C Polyurethane water dispersion (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; F-2160D-59)
  • PA Polyacrylic acid (Sigma Aldrich, molecular weight 15,000)
  • NMC LiNi 1/3 Co 1/3 Mn 1/3 O 2
  • LMO LiMn 2 O 4
  • LFP LiFePO 4
  • LCO LiCoO 2
  • a negative electrode slurry was prepared by mixing 4.0 g of a 50% by mass solution of a butadiene rubber aqueous dispersion (SBR) with a homodisper to obtain a solid content of 50%.
  • SBR butadiene rubber aqueous dispersion
  • the negative electrode was prepared in the same manner as the negative electrode 1 except that the types and blending amounts of the negative electrode active material, the conductive agent, the dispersion stabilizer, and the binder were changed as shown in Table 3 and Table 5, and the activities shown in Table 3 and Table 5 The negative electrode of the object mass was obtained.
  • (Positive electrode 1) 100 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NMC) which is a positive electrode active material, 7.8 g of acetylene black 5 g (made by Denka Co., Ltd., HS-100) as a conductive agent, cellulose fiber as a dispersion stabilizer 50 g of solid content is obtained by mixing 50 g of a 1 wt% aqueous dispersion of A-1 and 5.7 g of a 35 wt% solution of polyacrylic acid (manufactured by Sigma-Aldrich, molecular weight 15000) as a binder using a planetary mixer
  • the positive electrode slurry was prepared as follows. The positive electrode slurry was coated on a 15 ⁇ m thick electrolytic aluminum foil by a coating machine, dried at 130 ° C., and roll pressed to obtain a positive electrode active material of 13.8 mg / cm 2 .
  • the positive electrode 1 was prepared in the same manner as the positive electrode 1 except that the types and blending amounts of the positive electrode active material, the conductive agent, the dispersion stabilizer, and the binder were changed as shown in Table 4 and Table 6, and the activities shown in Table 4 and Table 6 An amount of positive electrode was obtained.
  • (Positive electrode 43) 100 g of LiNi 1/3 Co 1/3 Mn 1/3 O 2 which is a positive electrode active material, 7.8 g of acetylene black (made by Denka, HS-100) as a conductive agent, 6 g of polyvinylidene fluoride as a binder, and dispersed As a solvent, 61.3 g of N-methyl-2-pyrrolidone was mixed by a planetary mixer to prepare a positive electrode slurry so as to have a solid content of 65%. The positive electrode slurry was coated on a 15 ⁇ m thick aluminum foil by a coating machine, dried at 130 ° C., and roll pressed, to obtain a positive electrode of 13.8 mg / cm 2 of a positive electrode active material.
  • Cell impedance The cell impedance was measured for resistance at a frequency of 1 kHz using an impedance analyzer (SP-150 manufactured by biologic).
  • CC constant current charging is performed up to 4.2 V at a current density equivalent to 1 C. Then, after switching to CV (constant voltage) charging at 4.2 V and charging for 1.5 hours, 50 cycles of 20 C of CC discharge to 2.7 V at a current density equivalent to 1 C are performed, and the first time at this time The 1 C discharge capacity ratio after 50 cycles to the 1 C discharge capacity was taken as the 1 C charge / discharge cycle retention rate.
  • the dispersion stabilizer of the present invention can be used as a dispersion stabilizer for an electrode coating liquid of an electricity storage device, and the electrode produced therefrom is used for the production of various electricity storage devices.
  • the obtained power storage device can be used in various types of portable devices such as mobile phones, laptop computers, personal digital assistants (PDAs), video cameras, digital cameras, and medium- or large-sized power storage devices mounted on electric bicycles and electric vehicles. It can be used.

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Abstract

L'invention concerne une composition qui comprend un stabilisateur de dispersion pour un liquide de revêtement d'électrode pour un dispositif de stockage d'énergie, qui a une capacité supérieure à disperser de façon stable un matériau actif d'électrode et un matériau conducteur, et permet de fabriquer une électrode uniforme, même lorsqu'un dispositif de dispersion qui a une faible force de cisaillement est utilisé. Un dispersant pour un liquide de revêtement d'électrode pour un dispositif de stockage d'énergie, le dispersant étant caractérisé en ce qu'il contient des fibres de cellulose qui satisfont (a) – (c). (a) ont une largeur moyenne en nombre de largeur réduite de 2 à 200 nm. (b) ont un rapport d'aspect de 7,5 à 250. (c) comprend des cristaux de cellulose I qui ont une cristallinité de 70 % à 95 %.
PCT/JP2018/002045 2017-07-04 2018-01-24 Dispersant pour liquide de revêtement d'électrode, composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour liquide de revêtement d'électrode, et un dispositif de stockage d'énergie comprenant une électrode de dispositif de stockage d'énergie fabriquée à l'aide d'une composition liquide de revêtement d'électrode comprenant un dispersant pour un liquide de revêtement d'électrode WO2019008801A1 (fr)

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US16/624,912 US11437607B2 (en) 2017-07-04 2018-01-24 Dispersant for electrode coating liquid, electrode coating liquid composition including the dispersant for electrode coating liquid, electrode for power storage device manufactured using the electrode coating liquid composition, and power storage device having the electrode
CN201880042055.5A CN110896675B (zh) 2017-07-04 2018-01-24 电极涂覆液用分散剂、电极涂覆液组合物、蓄电装置用电极以及蓄电装置
KR1020197037165A KR102503911B1 (ko) 2017-07-04 2018-01-24 전극 도공액용 분산제, 그 전극 도공액용 분산제를 포함하는 전극 도공액 조성물, 그 전극 도공액 조성물을 사용하여 제작된 축전 디바이스용 전극, 및 그 전극을 구비하는 축전 디바이스

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JP6941637B2 (ja) * 2019-04-22 2021-09-29 第一工業製薬株式会社 電極用結着剤組成物、電極用塗料組成物、蓄電デバイス用電極、および蓄電デバイス
EP3961754A4 (fr) * 2019-04-22 2023-05-24 DKS Co. Ltd. Composition de liant pour électrode, composition de revêtement pour électrode, électrode pour dispositif de stockage d'énergie et dispositif de stockage d'énergie
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JP6856812B1 (ja) * 2020-10-21 2021-04-14 第一工業製薬株式会社 電極用結着剤組成物、電極用塗工液組成物、蓄電デバイス用電極及び蓄電デバイス

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JP7025852B2 (ja) 2022-02-25
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CN110896675A (zh) 2020-03-20
JP2019016457A (ja) 2019-01-31
US11437607B2 (en) 2022-09-06
KR20200024774A (ko) 2020-03-09

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